US5698601A - Process for the production of open-celled rigid polyurethane foams useful as insulating materials - Google Patents

Process for the production of open-celled rigid polyurethane foams useful as insulating materials Download PDF

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Publication number
US5698601A
US5698601A US08/636,731 US63673196A US5698601A US 5698601 A US5698601 A US 5698601A US 63673196 A US63673196 A US 63673196A US 5698601 A US5698601 A US 5698601A
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US
United States
Prior art keywords
cell
rigid polyurethane
open
closed
foams
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08/636,731
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English (en)
Inventor
Rainer Welte
Hans-Joachim Scholl
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Covestro LLC
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Bayer AG
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Publication of US5698601A publication Critical patent/US5698601A/en
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Assigned to COVESTRO LLC reassignment COVESTRO LLC CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: BAYER MATERIALSCIENCE LLC
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/38—Destruction of cell membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2330/00—Thermal insulation material
    • C08G2330/50—Evacuated open-celled polymer material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23—Sheet including cover or casing
    • Y10T428/231—Filled with gas other than air; or under vacuum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23—Sheet including cover or casing
    • Y10T428/233—Foamed or expanded material encased
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23—Sheet including cover or casing
    • Y10T428/239—Complete cover or casing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/24999—Inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers

Definitions

  • the present invention relates to a new process for the production of open-celled rigid foams and the use thereof as a filling material in vacuum insulation applications and airtight, closed, gas-filled foams.
  • EP-A 0,188,806 describes open-celled rigid polyurethane foams useful for the production of vacuum panelling which are made by reacting particular isocyanates with particular polyols in combination with particular stabilizers, cell openers and monofluorotrichloromethane (R11) as the expanding agent.
  • EP-A 0,581,191 discloses a method for producing open-celled, rigid polyurethane foams in which the expanding agent is an HCFC (i.e., a hydrogen-containing chlorofluorocarbon) or methylene chloride.
  • HCFC i.e., a hydrogen-containing chlorofluorocarbon
  • methylene chloride i.e., a hydrogen-containing chlorofluorocarbon
  • the present invention relates to a process for the production of completely open-celled rigid polyurethane foams.
  • closed-cell or partially closed-cell rigid polyurethane foams are converted into open-celled rigid polyurethane foams through the application of external pressure.
  • completely open-celled means that the percentage of open cells is greater than 96% which corresponds to a state of fully open cells within the accuracy of the method used to determine open cell content.
  • the closed-cell or partially closed-cell rigid polyurethane foam used as the starting material in the process of the present invention is produced in a mold in accordance with any of the molding techniques known to those skilled in the art.
  • the mold walls should preferably be such that an airtight barrier such as a film or coating can be formed or applied to the rigid, closed-cell foam present within the mold.
  • the closed cells of the foam are opened while the foam is still within the mold by applying external pressure.
  • the present invention also relates to the open-celled rigid polyurethane foams produced by the process of the present invention.
  • These open-cell rigid foams are particularly useful as filling material in evacuated insulating panels especially when the foam is coated with an airtight film made of plastic or metal or made of composite films of plastic or plastics and metal or metals or glass or ceramic materials prior to evacuation (i.e., opening of the foam cell walls).
  • the foams of the present invention are also useful as insulating foams which are resistant to shrinkage; as filling material in airtight insulating panels when the foam is filled with an insulating gas which is heavier than air (preferably a heavy insulating gas which is virtually insoluble in the cell material) after the closed cells have been opened; as insulating material in refrigerators, in refrigerator vehicles, in freezers, freezing vehicles, containers, freezing counters, cooling counters, hot water containers and containers used in industrial construction and in the heat-distributing industry.
  • the present invention also relates to an evacuated insulating panel which is made up of a) an open-celled rigid polyurethane foam obtained in accordance with the present invention and b) an airtight coating film made of b1) plastic or metal or b2) made of a composite film of plastic or plastics and metal or metals or b3) glass compositions or b4) ceramic compositions.
  • the present invention also relates to Insulating panels filled with an insulating gas which is heavier than air, which are made up of a) an open-celled rigid polyurethane foam produced by applying external pressure to a rigid, closed-cell foam and b) an airtight coating film made of b1) plastic or metal or b2) made of a composite film of plastic or plastics and metal or metals or b3) glass compositions or b4) ceramic compositions.
  • the cell walls are destroyed by "blowing off”in the final stages of prior art processes for the production of open-celled polyurethane foams.
  • the open-celled rigid polyurethane foams of the present invention may, however, also be used as insulating materials in panels at normal pressure or in the range between high vacuum and normal pressure, if the cells are filled with a heavy gas (that is, a gas which is heavier than air) such as a heavy rare gas, an organic volatile gas, a CFC or a fluorocarbon.
  • a heavy gas that is, a gas which is heavier than air
  • a heavy rare gas such as a heavy rare gas, an organic volatile gas, a CFC or a fluorocarbon.
  • CFC expanding agents may no longer be used in conventional insulating materials because they enter the atmosphere by diffusion or during destruction and disposal of old appliances.
  • CFCs can be used without problems in open-celled foams having airtight external coats because the CFCs do not diffuse into the atmosphere and can be readily liberated by evacuation during disposal.
  • any of the starting materials known by those skilled in the art to be useful in the production of rigid polyurethane foams containing at least some closed cells may be used to produce the closed cell foams used in the practice of the present invention.
  • Methods and materials useful for the production of closed-cell, rigid polyurethane foams are disclosed, for example, in Kunststoff-Handbuch, Volume VII, "Polyurethanes", edited by G. Oertel (Publisher Carl Hanser, Kunststoff 1993), pages 267 ff.
  • the closed-cell or partly closed-cell rigid foams used as the starting material in the practice of the present invention generally have bulk densities in the range of from about 20 to about 200 kg/m 3 , preferably from about 30 to about 100 kg/m 3 .
  • the conversion of the closed-cell rigid foams into the corresponding, completely open-celled rigid polyurethane foams in accordance with the present invention is accomplished by applying external pressure, for example, in pressure chambers.
  • the amount of pressure to be applied and the period of application depend upon the particular closed-cell rigid foam being used.
  • the amount of pressure and length of time such pressure should be applied may easily be determined by a simple preliminary experiment. Generally, pressures of from about 2 to about 20 bar for from about 1 to about 60 seconds are sufficient.
  • a conventional rigid polyurethane foam having a bulk density of 50 kg/m 3 and a percentage of closed cells of more than 90% (DIN-ISO 4590) was exposed for 5 seconds to an excess pressure of I bar.
  • the percentage of open cells was then determined to be more than 96%, which, within the limits of accuracy of the method used to determine the open cell content, corresponds to a state of fully open cells. Longer residence times of 10 seconds, 2 minutes, 10 minutes or 30 minutes produced foams with identical open cell contents.
  • Example 2 The same foam as in Example 1 was exposed to a pressure of 10 bars, with the increase in pressure taking place on a first sample within 5 seconds, on a second sample within 2 minutes and on a third sample within 30 minutes. All three samples had the same percentage of open cells, more than 96%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Cell Biology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Thermal Insulation (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Molding Of Porous Articles (AREA)
  • Building Environments (AREA)
US08/636,731 1994-05-27 1996-04-19 Process for the production of open-celled rigid polyurethane foams useful as insulating materials Expired - Lifetime US5698601A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/636,731 US5698601A (en) 1994-05-27 1996-04-19 Process for the production of open-celled rigid polyurethane foams useful as insulating materials

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4418507A DE4418507A1 (de) 1994-05-27 1994-05-27 Verfahren zur Herstellung offenzelliger Polyurethan-Hartschaumstoffe und ihre Verwendung als Isoliermaterial in Paneelen und als Isolierschaumstoffe
DE4418507.3 1994-05-27
US44350395A 1995-05-18 1995-05-18
US08/636,731 US5698601A (en) 1994-05-27 1996-04-19 Process for the production of open-celled rigid polyurethane foams useful as insulating materials

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US44350395A Division 1994-05-27 1995-05-18

Publications (1)

Publication Number Publication Date
US5698601A true US5698601A (en) 1997-12-16

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US08/636,731 Expired - Lifetime US5698601A (en) 1994-05-27 1996-04-19 Process for the production of open-celled rigid polyurethane foams useful as insulating materials

Country Status (15)

Country Link
US (1) US5698601A (fr)
EP (1) EP0685512B1 (fr)
JP (1) JPH0859879A (fr)
KR (1) KR100349270B1 (fr)
CN (1) CN1126138A (fr)
AT (1) ATE195542T1 (fr)
BR (1) BR9502564A (fr)
CA (1) CA2149851A1 (fr)
CZ (1) CZ290983B6 (fr)
DE (2) DE4418507A1 (fr)
DK (1) DK0685512T3 (fr)
ES (1) ES2151003T3 (fr)
HU (1) HU216068B (fr)
PT (1) PT685512E (fr)
SI (1) SI0685512T1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6020391A (en) * 1996-11-08 2000-02-01 Imperial Chemical Industries Plc Flexible polyurethane foams
US6067765A (en) * 1997-02-21 2000-05-30 Msx, Inc. Insulated layer of concrete
US6147134A (en) * 1996-11-08 2000-11-14 Imperial Chemical Industries Plc Process for preparing rigid and flexible polyurethane foams
US6235806B1 (en) 1998-06-26 2001-05-22 Nisshinbo Industries, Inc. Open-celled rigid polyurethane foam and method for producing the same
US6322743B1 (en) 1998-01-19 2001-11-27 Imperial Chemical Industries Plc Method of forming evacuated insulation panels
EP1205501A1 (fr) * 2000-11-09 2002-05-15 Huntsman International Llc Procédé pour la préparation de mousse de polyuréthane rigide ou mousse de polyisocyanurate modifié par uréthane et mousse ainsi préparée
US6756416B2 (en) 2002-02-12 2004-06-29 Foamex L.P. Hydrophilic ester polyurethane foams
US20040162361A1 (en) * 2002-02-12 2004-08-19 Foamex L.P. Felted hydrophilic ester polyurethane foams
US20050076996A1 (en) * 2003-10-08 2005-04-14 Mitsumagiken Co., Ltd. Method for manufacturing open cell rubber material and method for manufacturing rubber roller
US20070191502A1 (en) * 2006-02-14 2007-08-16 Foamex L.P. Hydrophilic ester polyurethane foams
US20070266613A1 (en) * 2006-05-19 2007-11-22 Nelson Barry J Decoy portions and decoys comprising rigid polyurethane, and related methods
US20090264549A1 (en) * 2008-04-21 2009-10-22 Foamex L.P. Variable felted polyurethane foams for sponges and wipes
US8418297B2 (en) 2005-06-24 2013-04-16 Tempur-Pedic Management, Llc Reticulated material body support and method

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ335218A (en) 1996-11-08 2000-11-24 Huntsman Ici Chem Llc Process for making flexible polyurethane foams
KR20000053117A (ko) * 1996-11-08 2000-08-25 네바드 에드워드 죤 경질 및 연질 폴리우레탄 발포체의 제조 방법
DE19758219A1 (de) * 1997-12-31 1999-07-01 Uvt Umwelt Und Verfahrens Tech Vakuumisolationspaneel
JPH11346776A (ja) * 1998-06-11 1999-12-21 Ajinomoto Co Inc ブレビバクテリウム・ラクトファーメンタムのシトクロムｂｄ型キノールオキシダーゼ遺伝子
DE19917787A1 (de) * 1999-04-20 2000-11-02 Bayer Ag Komprimierte Polyurethanhartschaumstoffe
KR100314431B1 (ko) * 1999-04-23 2001-11-15 구자홍 진공단열재 코어의 제조방법
JP4925504B2 (ja) * 2000-10-13 2012-04-25 株式会社日本触媒 多孔質重合体の製造方法
BR112013019576A2 (pt) * 2011-03-04 2017-06-13 Basf Se elemento compósito, processo para produzir elementos compósitos, e, uso dos elementos compósitos.
CN108506646B (zh) * 2017-02-28 2024-04-26 芜湖美的厨卫电器制造有限公司 保温型材及热水器
MX2020005325A (es) 2017-11-28 2020-08-13 Dow Global Technologies Llc Panel de aislamiento a base de poliuretano.
MX2020005321A (es) 2017-11-28 2020-08-13 Dow Global Technologies Llc Tablero para aislamiento de espuma de poliuretano/poliisocianurato reforzado con fibra de vidro.

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GB2040948A (en) * 1979-01-30 1980-09-03 Roth Sa Freres Method of making a sound-absorbent material and material so made
EP0184415A1 (fr) * 1984-12-04 1986-06-11 Nippon Sanso Kabushiki Kaisha Module d'isolation thermique utilisant le vide
US4668555A (en) * 1984-12-27 1987-05-26 Matsushita Refrigeration Co. Heat insulating body
EP0231820A2 (fr) * 1986-02-04 1987-08-12 CREST-FOAM Corp. Table de support pour une machine à découper et méthode pour sa fabrication
US5083361A (en) * 1988-02-05 1992-01-28 Robert C. Bogert Pressurizable envelope and method
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US5350777A (en) * 1992-07-27 1994-09-27 Matsushita Refrigeration Company Production and use of open cell rigid polyurethane foam

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Publication number Priority date Publication date Assignee Title
DE139265C (fr) *
GB2040948A (en) * 1979-01-30 1980-09-03 Roth Sa Freres Method of making a sound-absorbent material and material so made
EP0184415A1 (fr) * 1984-12-04 1986-06-11 Nippon Sanso Kabushiki Kaisha Module d'isolation thermique utilisant le vide
US4668555A (en) * 1984-12-27 1987-05-26 Matsushita Refrigeration Co. Heat insulating body
EP0231820A2 (fr) * 1986-02-04 1987-08-12 CREST-FOAM Corp. Table de support pour une machine à découper et méthode pour sa fabrication
US5083361A (en) * 1988-02-05 1992-01-28 Robert C. Bogert Pressurizable envelope and method
US5318997A (en) * 1992-04-20 1994-06-07 Takeda Chemical Industries, Ltd. Method for production of open cell rigid polyurethane foam
US5350777A (en) * 1992-07-27 1994-09-27 Matsushita Refrigeration Company Production and use of open cell rigid polyurethane foam

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6020391A (en) * 1996-11-08 2000-02-01 Imperial Chemical Industries Plc Flexible polyurethane foams
US6147134A (en) * 1996-11-08 2000-11-14 Imperial Chemical Industries Plc Process for preparing rigid and flexible polyurethane foams
US6288134B1 (en) * 1996-11-08 2001-09-11 Imperial Chemical Industries Plc Flexible polyurethane foams
US6346204B1 (en) 1996-11-08 2002-02-12 Huntsman International Llc Process for preparing rigid and flexible polyurethane foams
US6067765A (en) * 1997-02-21 2000-05-30 Msx, Inc. Insulated layer of concrete
US6322743B1 (en) 1998-01-19 2001-11-27 Imperial Chemical Industries Plc Method of forming evacuated insulation panels
US6235806B1 (en) 1998-06-26 2001-05-22 Nisshinbo Industries, Inc. Open-celled rigid polyurethane foam and method for producing the same
EP1205501A1 (fr) * 2000-11-09 2002-05-15 Huntsman International Llc Procédé pour la préparation de mousse de polyuréthane rigide ou mousse de polyisocyanurate modifié par uréthane et mousse ainsi préparée
US6756416B2 (en) 2002-02-12 2004-06-29 Foamex L.P. Hydrophilic ester polyurethane foams
US20040162361A1 (en) * 2002-02-12 2004-08-19 Foamex L.P. Felted hydrophilic ester polyurethane foams
US6841586B2 (en) 2002-02-12 2005-01-11 Foamex, L.P. Felted hydrophilic ester polyurethane foams
US20050076996A1 (en) * 2003-10-08 2005-04-14 Mitsumagiken Co., Ltd. Method for manufacturing open cell rubber material and method for manufacturing rubber roller
US7384490B2 (en) * 2003-10-08 2008-06-10 Mitsumagiken Co. Ltd. Method for manufacturing open cell rubber material and method for manufacturing rubber roller
US8418297B2 (en) 2005-06-24 2013-04-16 Tempur-Pedic Management, Llc Reticulated material body support and method
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DK0685512T3 (da) 2000-10-23
KR100349270B1 (ko) 2002-11-01
ES2151003T3 (es) 2000-12-16
HU9501545D0 (en) 1995-07-28
SI0685512T1 (en) 2000-10-31
JPH0859879A (ja) 1996-03-05
ATE195542T1 (de) 2000-09-15
PT685512E (pt) 2001-01-31
KR950032398A (ko) 1995-12-20
CZ135695A3 (en) 1995-12-13
CN1126138A (zh) 1996-07-10
HUT72093A (en) 1996-03-28
DE4418507A1 (de) 1995-11-30
HU216068B (hu) 1999-04-28
BR9502564A (pt) 1996-03-05
DE59508635D1 (de) 2000-09-21
EP0685512B1 (fr) 2000-08-16
CA2149851A1 (fr) 1995-11-28
CZ290983B6 (cs) 2002-11-13
EP0685512A1 (fr) 1995-12-06

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